WO2017186577A1 - Composition agrochimique granulaire de type à libération lente et son procédé de fabrication - Google Patents

Composition agrochimique granulaire de type à libération lente et son procédé de fabrication Download PDF

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Publication number
WO2017186577A1
WO2017186577A1 PCT/EP2017/059430 EP2017059430W WO2017186577A1 WO 2017186577 A1 WO2017186577 A1 WO 2017186577A1 EP 2017059430 W EP2017059430 W EP 2017059430W WO 2017186577 A1 WO2017186577 A1 WO 2017186577A1
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Prior art keywords
methyl
composition
carrier
binder
primary granules
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PCT/EP2017/059430
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English (en)
Inventor
Holger Egger
Masanori OI
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Bayer Cropscience Aktiengesselschaft
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Application filed by Bayer Cropscience Aktiengesselschaft filed Critical Bayer Cropscience Aktiengesselschaft
Priority to US16/096,608 priority Critical patent/US20190133118A1/en
Priority to CN201780040718.5A priority patent/CN109310082B/zh
Priority to JP2018556436A priority patent/JP7204486B2/ja
Priority to KR1020187034410A priority patent/KR102538200B1/ko
Publication of WO2017186577A1 publication Critical patent/WO2017186577A1/fr
Priority to PH12018502244A priority patent/PH12018502244A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to a "timed-release-type granular agrochemical composition" and a method for manufacturing the same, intended to mitigate chemical phytotoxicity to crops and sustain agrochemical potency.
  • Japanese Laid-Open Patent Application 9-143005 discloses an invention relating to a timed-disintegration-type multilayer coated agrochemical granular formulation in which the surface of a granular body having a water-swelling substance as a main component is coated with a composition comprising an agrochemical active ingredient and a thermoplastic resin, wherein the surface of the coated agrochemical granular formulation is further coated with a coating material having an olefin polymer or a copolymer thereof as a main component.
  • Japanese Laid-Open Patent Application 2003-183104 discloses an invention relating to a coated bioactive substance formed by coating the surface of bioactive substance particles with polyurethane obtained by reacting an isocyanate with a mixture of a polyol having a hydroxyl equivalent of 120 or less and a polyol having a hydroxyl equivalent of 150 or more. Both of these inventions involve coating primary granules with polymers, thereby enabling timed release. However, heating and drying are necessary in the coating step for coating polymers sufficient for the timed release of the agrochemical active ingredient or bioactive substance, and expensive manufacturing apparatuses provided with devices for heating and drying are also necessary; therefore, the coating step could take a long time, and the actual manufacturing costs could be quite high. Both patent applications are directed to film forming technology and do not disclose or suggest the powder coating technology of the present invention.
  • Japanese Laid-Open Patent Application 2007-176920 discloses an invention relating to a granular composition formed by coating primary granules using a mixed composition containing a pest-control active compound, a polymer resin, a hydrophobic substance, talc, a water-soluble substance, and, depending on the circumstances, the other formulants.
  • JP 2003 171207 A, WO 2005/029956 Al, US 2014/162880 Al and CN 1 684 583 A disclose controlled release granular agrochemical compositions, however those granules cannot undergo timed release.
  • US 6 046 277 A discloses a controlled release granular pharmaceutical and agrochemical composition.
  • Patent Reference 1 Japanese Laid-Open Patent Application 9-143005
  • Patent Reference 2 Japanese Laid-Open Patent Application 2003-183104
  • Patent Reference 3 Japanese Laid-Open Patent Application 2007-176920
  • the present invention relates to a timed-release-type granular agrochemical composition formed by coating primary granules that comprise a mixed composition containing an agrochemical active ingredient, a swelling agent, a surfactant, and, depending on the circumstances, the other formulants; the primary granules being coated with a mixed composition containing a binder, a hydrophobic substance, a carrier, and, depending on the circumstances, the other formulants.
  • Timed-release in the present invention is defined as limited release of active ingredient for several days followed by a sharp release of the active ingredient drawing sigmoid curve.
  • timed-release can be defined as "no release of active ingredient until the disintegration of the granule takes palce” or "no disintegration of the granule for several days". By using more granules, the disintegration/release curve will become a sigmoid curve, but if "no disintegration” or “no release” is still observed for a certain period, it is considered to be timed-release.
  • One aspect of the present invention relates to a timed-release-type granular agrochemical composition formed by coating primary granules that comprise at least one type of agrochemical active ingredient a), a swelling substance b), and, depending on the circumstances, a carrier c), a surfactant d), and/or the other formulants g); the primary granules being coated with a binder e), a hydrophobic substance f), a carrier c), and, depending on the circumstances, the other formulants g).
  • the present invention is also directed to timed-release-type granular agrochemical compositions containing coated primary granules wherein the primary granules contain at least one agrochemical active ingredient a), one or more swelling agents b), one or more carrier c), one or more surfactants d) and the primary granules are coated with at least one binder e), one or more hydrophobic substance f) and one or more carrier c).
  • the primary granules contain at least one agrochemical active ingredient a), one or more swelling agents b), one or more carrier c), one or more surfactants d) and other formulants g).
  • Another aspect of the present invention relates to the aforementioned composition, wherein the swelling agent b) is selected from among bentonite, starch, glucomannan and water-absorbent polymers.
  • the surfactant d) is selected from among anionic surfactants, non-ionic surfactants, amphoteric surfactants, and cationic surfactants.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the binder e) comprises a combination of a polyol and a polyisocyanate.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the binder e) comprises a combination of a polyamine and a polyisocyanate.
  • polyol is selected from among polyether polyols, polyester polyols, polybutadiene polyols, polycarbonate polyols, and castor-oil-based (triglyceride-based) polyols.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the polyamine is selected from among polyaspartic acid esters.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the polyisocyanate is selected from among aromatic polyisocyanates and aliphatic polyisocyanates.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the hydrophobic substance f) is selected from among calcium stearate, magnesium stearate, and aluminum stearate.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the carrier c) is selected from among clay, powdered pumice, burned diatomaceous earth, kaolin, talc, acid clay, and calcium carbonate.
  • the carrier c) is selected from among clay, powdered pumice, burned diatomaceous earth, kaolin, talc, acid clay, and calcium carbonate.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the primary granules contain c) clay.
  • Another aspect of the present invention relates to the aforementioned composition, wherein the coating of the primary granules contains a mixture of c) talc and f) calcium stearate.
  • Another aspect of the present invention relates to a method for manufacturing the aforementioned timed-release-type granular agrochemical composition, the method comprising the following steps: a first step for charging primary granules that comprise at least one type of agrochemical active compound a), a swelling substance b), and, depending on the circumstances, a carrier c), a surfactant d), and the other formulants into a tumbling- or centrifugal-tumbling-type granulator/mixer; a second step for performing tumbling while adding a binder e) and a hydrophobic substance f) in alternating fashion or simultaneously; a third step for performing tumbling while adding a binder e) and a carrier c) in alternating fashion or simultaneously, and then forming an outermost layer; and a fourth step for heating the granular composition as needed.
  • the present invention is also directed to a method for preparing timed-release-type granular agrochemical compositions, characterized in that in a first step the primary granules are prepared by granulating a mixture of an agrochemical active ingredient a), a swelling agent b), a carrier c), a surfactant d); - in a second step the primary granules of the first step are coated with the hydrophobic substance f) or a mixture of the hydrophobic substance f) and the carrier c) and the binder e) without heating.
  • the primary granules are prepared by granulating a mixture of an agrochemical active ingredient a), a swelling agent b), a carrier c), a surfactant d) and other formulants g).
  • the performance of the coating is repeated by using the binder e) and the hydrophobic substance f) in alternating fashion, or charging the hydrophobic substance f) while spraying the binder e).
  • the performance of the coating is repeated by using the binder e) and the carrier c) in alternating fashion, or charging the carrier c) while spraying the binder e).
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the swelling agent b) is selected from among bentonite, starch, glucomannan and water- absorbent polymers.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the surfactant d) is selected from among anionic surfactants, non-ionic surfactants, amphoteric surfactants, and cationic surfactants.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the binder e) comprises a combination of a polyol and a polyisocyanate.
  • binder e comprises a combination of a polyamine and a polyisocyanate.
  • polyol is selected from among polyether polyols, polyester polyols, polybutadiene polyols, polycarbonate polyols, and castor-oil-based (triglyceride-based) polyols.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the polyamine is selected from among polyaspartic acid esters.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the polyisocyanate is selected from among aromatic polyisocyanates and aliphatic polyisocyanates.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the hydrophobic substance f) is selected from among calcium stearate, magnesium stearate, and aluminum stearate.
  • Another aspect of the present invention relates to the aforementioned manufacturing method, wherein the carrier c) is selected from among clay, powdered pumice, burned diatomaceous earth, kaolin, talc, acid clay, and calcium carbonate.
  • the primary granules are coated with a mixture of c) talc and f) calcium stearate.
  • a timed-release-type granular agrochemical agent in which the release of the active ingredient is effectively controlled, whereby an exceptional biological effect lasts over a long period of time, and chemical phytotoxicity to useful plants can be mitigated.
  • the present invention makes it possible to expect the mitigation of chemical phytotoxicity to young rice plants when applied to a nursery box as an insecticide/fungicide or to a water surface as an herbicide, and the continuation of biological effects after transplantation of rice seedling.
  • rice cultivation is not cited by way of limitation; the present invention can be applied to all varieties of spaces where systemic chemical formulations are applied; i.e., to application of a chemical formulation in an upland field crop under non-flooded conditions.
  • the present invention is a granular agrochemical agent obtained by "powder coating," the weight of the hydrophobic substance exceeding the weight of the binder.
  • agrochemical active compound a) should be understood to refer to all substances that typically are or can be used to treat plants.
  • Preferred examples of the agrochemical active compound a) include fungicides, bactericides, insecticides, acaricides, nematicides, molluscicides, herbicides, safeners, plant growth regulators, and plant nutrients, as well as biological control agents.
  • fungicides which may be mentioned are: Group 1 :
  • Inhibitors of the ergosterol biosynthesis for example (1.1) aldimorph, (1.2) azaconazole, (1.3) bitertanol, (1.4) bromuconazole, (1.5) cyproconazole, (1.6) diclobutrazole, (1.7) difenoconazole, (1.8) diniconazole, (1.9) diniconazole-M, (1.10) dodemorph, (1.1 1) dodemorph acetate, (1.12) epoxiconazole, (1.13) etaconazole, (1.14) fenarimol, (1.15) fenbuconazole, (1.16) fenhexamid, (1.17) fenpropidin, (1.18) fenpropimorph, (1.19) fluquinconazole, (1.20) flurprimidol, (1.21) flusilazole, (1.22) flutriafol, (1.23) furconazole, (1.24) furconazole-cis, (
  • Inhibitors of the respiratory chain at complex I or II for example (2.1) bixafen, (2.2) boscalid, (2.3) carboxin, (2.4) diflumetorim, (2.5) fenfuram, (2.6) fluopyram, (2.7) flutolanil, (2.8) fluxapyroxad, (2.9) furametpyr, (2.10) furmecyclox, (2.11) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.12) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.13) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.14) isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), (2.15) isopyrazam (syn epimeric racemate 1RS,4SR,9RS
  • Inhibitors of the respiratory chain at complex III for example (3.1) ametoctradin, (3.2) amisulbrom, (3.3) azoxystrobin, (3.4) cyazofamid, (3.5) coumethoxystrobin, (3.6) coumoxystrobin, (3.7) dimoxystrobin, (3.8) enoxastrobin, (3.9) famoxadone, (3.10) fenamidone, (3.11) flufenoxystrobin, (3.12) fluoxastrobin, (3.13) kresoxim-methyl, (3.14) metominostrobin, (3.15) orysastrobin, (3.16) picoxystrobin, (3.17) pyraclostrobin, (3.18) pyrametostrobin, (3.19) pyraoxystrobin, (3.20) pyribencarb, (3.21) triclopyricarb, (3.22) trifloxystrobin, (3.23) (2E)-2-(2- ⁇ [6-(3-ch
  • Inhibitors of the mitosis and cell division for example (4.1) benomyl, (4.2) carbendazim, (4.3) chlorfenazole, (4.4) diethofencarb, (4.5) ethaboxam, (4.6) fluopicolide, (4.7) fuberidazole, (4.8) pencycuron, (4.9) thiabendazole, (4.10) thiophanate-methyl, (4.11) thiophanate, (4.12) zoxamide, (4.13) 5-chloro-7-(4-methylpiperidin-l-yl)-6-(2,4,6 rifluorophenyl)[l,2,4]triazolo[l,5-a]pyrimidine, (4.14) 3- chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine;
  • Group 5 Compounds capable to have a multisite action, for example (5.1) bordeaux mixture, (5.2) captafol, (5.3) captan, (5.4) chlorothalonil, (5.5) copper hydroxide, (5.6) copper naphthenate, (5.7) copper oxide, (5.8) copper oxychloride, (5.9) copper(2+) sulfate, (5.10) dichlofluanid, (5.11) dithianon, (5.12) dodine, (5.13) dodine free base, (5.14) ferbam, (5.15) fluorofolpet, (5.16) folpet, (5.17) guazatine, (5.18) guazatine acetate, (5.19) iminoctadine, (5.20) iminoctadine albesilate, (5.21) iminoctadine triacetate, (5.22) mancopper, (5.23) mancozeb, (5.24) maneb, (5.25) metiram, (5.26) metiram zinc, (5.27)
  • Compounds capable to induce a host defence for example (6.1) acibenzolar-S-methyl, (6.2) isotianil, (6.3) phosphonate, (6.4) fosetyl-aluminium, (6.5) probenazole, (6.6) saccharine, (6.7) tiadinil, (6.8) 2,6- dichloroiso nicotinic acid, (6.9) 3,5-dichloroanthranilic acid, (6.10) beta-aminobutyric acid, (6.10) laminarin, (6.11) beta-glucans, (6.12) heptamaloxyloglucan, (6.13) rhamno lipids, (6.14) chitin or chitin fragments; (6.15) lipochitooligosaccharides, (6.16) harpin protein, (6.17) humic acids, (6.18) lignin fragments; preferably (6.1) acibenzolar-S-methyl, (6.2) isotianil, (6.5) probenazole, (
  • Inhibitors of the amino acid or protein biosynthesis for example (7.1) andoprim, (7.2) blasticidin-S, (7.3) cyprodinil, (7.4) kasugamycin, (7.5) kasugamycin hydrochloride hydrate, (7.6) mepanipyrim, (7.7) pyrimethanil, (7.8) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-l -yl)quinoline, (7.9) oxytetracycline, (7.10) streptomycin;
  • Inhibitors of the ATP production for example (8.1) fentin acetate, (8.2) fentin chloride, (8.3) fentin hydroxide, (8.4) silthiofam; Group 9:
  • Inhibitors of the cell wall synthesis for example (9.1) benthiavalicarb, (9.2) dimethomorph, (9.3) flumorph, (9.4) iprovalicarb, (9.5) mandipropamid, (9.6) polyoxins, (9.7) polyoxorim, (9.8) validamycin A, (9.9) valifenalate, (9.10) polyoxin B;
  • Group 10 Inhibitors of the lipid and membrane synthesis, for example (10.1) biphenyl, (10.2) chloroneb, (10.3) dicloran, (10.4) edifenphos, (10.5) etridiazole, (10.6) iodocarb, (10.7) iprobenfos, (10.8) isoprothiolane, (10.9) propamocarb, (10.10) propamocarb hydrochloride, (10.1 1) prothiocarb, (10.12) pyrazophos, (10.13) quintozene, (10.14) tecnazene, (10.15) tolclofos-methyl;
  • Group 1 1 Inhibitors of the melanin biosynthesis, for example (1 1.1) carpropamid, (1 1.2) diclocymet, (1 1.3) fenoxanil, (1 1.4) phthalide, (1 1.5) pyroquilon, (1 1.6) tricyclazole, (1 1.7) 2,2,2-trifluoroethyl ⁇ 3-methyl- l -[(4-methylbenzoyl)amino]butan-2-yl ⁇ carbamate;
  • Inhibitors of the nucleic acid synthesis for example (12.1 ) benalaxyl, (12.2) benalaxyl-M (kiralaxyl), (12.3) bupirimate, (12.4) clozylacon, (12.5) dimethirimol, (12.6) ethirimol, (12.7) furalaxyl, (12.8) hymexazol, (12.9) metalaxyl, (12.10) metalaxyl-M (mefenoxam), (12.1 1) ofurace, (12.12) oxadixyl, (12.13) oxolinic acid, (12.14) octhilinone;
  • Inhibitors of the signal transduction for example (13.1) chlozolinate, (13.2) fenpiclonil, (13.3) fludioxonil, (13.4) iprodione, (13.5) procymidone, (13.6) quinoxyfen, (13.7) vinclozolin, (13.8) proquinazid;
  • Examples preferably include (systemic) fungicides having a octanol/water partition coefficient (LogPow) of 5 or less.
  • Examples of the preferred fungicides which may be mentioned are: inhibitors of the respiratory chain at complex I or II (group 2), inhibitors of the respiratory chain at complex III (group 3), compounds capable to induce a host defence (group 6), inhibitors of the lipid and membrane synthesis (group 10) and inhibitors of the melanin biosynthesis (group 11).
  • Examples of the most preferred fungicides which may be mentioned are: probenazole, tiadinil, isotianil, furametpyr, thifluzamide, penflufen, orysastrobin, azoxystrobin, metominostrobin, carpropamid, fenoxanil, diclocymet, tricyclazole, isoprothiolane, tolprocarb and pyroquilon.
  • bactericides which may be mentioned are: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • insecticides, acaricides and nematicides which may be mentioned are:
  • Acetylcholinesterase (AChE) inhibitors for example carbamates, e.g. alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, and xylylcarb; or organophosphates, e.g.
  • GABA-gated chloride channel antagonists for example organochlorines, e.g. camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, and methoxychlor; or fiproles (phenylpyrazoles), e.g. acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, and vaniliprole.
  • organochlorines e.g. camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, and methoxychlor
  • fiproles phenylpyrazoles
  • Sodium channel modulators/voltage-dependent sodium channel blockers for example pyrethroids, e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin S- cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, deltamethrin, empenthrin (1R isomer), esfenvalerate
  • Nicotinergic acetylcholine receptor agonists/antagonists for example chloronicotinyls, e.g. acetamiprid, clothianidin, dinotefuran, flupyradifurone, imidacloprid, imidaclothiz, nitenpyram, nithiazine, thiacloprid, thiamethoxam, AKD-1022; or nicotine, bensultap, cartap, thiosultap-sodium, and thiocylam.
  • chloronicotinyls e.g. acetamiprid, clothianidin, dinotefuran, flupyradifurone, imidacloprid, imidaclothiz, nitenpyram, nithiazine, thiacloprid, thiamethoxam, AKD-1022; or nicotine, bensultap, cartap, thiosultap-sodium, and
  • Allosteric acetylcholine receptor modulators for example spinosyns, e.g. spinosad and spinetoram.
  • Chloride channel activators for example mectins/macrolides, e.g. abamectin, emamectin, emamectin benzoate, ivermectin, lepimectin, and milbemectin; or juvenile hormone analogues, e.g. hydroprene, kinoprene, methoprene, epofenonane, triprene, fenoxycarb, pyriproxifen, and diofenolan.
  • mectins/macrolides e.g. abamectin, emamectin, emamectin benzoate, ivermectin, lepimectin, and milbemectin
  • juvenile hormone analogues e.g. hydroprene, kinoprene, methoprene, epofenonane, triprene, fenoxycarb,
  • Active ingredients with unknown or non-specific mechanisms of action for example gassing agents, e.g. methyl bromide, chloropicrin and sulfuryl fluoride; selective antifeedants, e.g. cryolite, pymetrozine, pyrifluquinazon and flonicamid; or mite growth inhibitors, e.g. clofentezine, hexythiazox, etoxazole.
  • gassing agents e.g. methyl bromide, chloropicrin and sulfuryl fluoride
  • selective antifeedants e.g. cryolite, pymetrozine, pyrifluquinazon and flonicamid
  • mite growth inhibitors e.g. clofentezine, hexythiazox, etoxazole.
  • Oxidative phosphorylation inhibitors, ATP disrupters for example diafenthiuron; organotin compounds, e.g. azocyclotin, cyhexatin and fenbutatin oxide; or propargite, tetradifon.
  • organotin compounds e.g. azocyclotin, cyhexatin and fenbutatin oxide
  • propargite tetradifon.
  • Oxidative phoshorylation decouplers acting by interrupting the H proton gradient for example chlorfenapyr, binapacryl, dinobuton, dinocap and DNOC.
  • Microbial disruptors of the insect gut membrane for example Bacillus thuringiensis strains.
  • Chitin biosynthesis inhibitors for example benzoylureas, e.g. bistrifluron, chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, novi- flumuron, penfluron, teflubenzuron or triflumuron.
  • benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, novi- flumuron, penfluron, teflubenzuron or triflumuron.
  • Ecdysone agonists/disrupters for example diacylhydrazines, e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and Fufenozide (JS118); or azadirachtin.
  • diacylhydrazines e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and Fufenozide (JS118); or azadirachtin.
  • Octopaminergic agonists for example amitraz.
  • Site III electron transport inhibitors/site II electron transport inhibitors for example hydramethylnon; acequinocyl; fluacrypyrim; or cyflumetofen and cyenopyrafen.
  • Electron transport inhibitors for example Site I electron transport inhibitors, from the group of the METI acaricides, e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, and rotenone; or voltage-dependent sodium channel blockers, e.g. indoxacarb and metaflumizone.
  • METI acaricides e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, and rotenone
  • voltage-dependent sodium channel blockers e.g. indoxacarb and metaflumizone.
  • Fatty acid biosynthesis inhibitors for example tetronic acids such as spirodiclofen and spiromesifen; or tetramic acids such as spirotetramat.
  • Neuronal inhibitors with unknown mechanism of action e.g. bifenazate.
  • Ryanodine receptor effectors for example diamides, e.g. flubendiamide, (R),(S)-3-chloro-N 1 - ⁇ 2- methyl-4- [ 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl ⁇ -N 2 -( 1 -methyl-2-methylsulphonyl- ethyl)phthalamide, chlorantraniliprole (Rynaxypyr), tetraniliprole, or Cyantraniliprole (Cyazypyr).
  • diamides e.g. flubendiamide
  • Examples preferably include (systematic) insecticides having a LogPow of 5 or less.
  • Examples the preferred insecticides which may be mentioned are: (1) Acetylcholinesterase (AChE) inhibitors, (2) GABA-gated chloride channel antagonists, (3) Sodium channel modulators/voltage-dependent sodium channel blockers, (4) Nicotinergic acetylcholine receptor agonists/antagonists, (5) Allosteric acetylcholine receptor modulators (agonists), (7) selective antifeedants, (11) Chitin biosynthesis inhibitors (18), fatty acid biosynthesis inhibitors and (20) Ryanodine receptor effectors.
  • AChE Acetylcholinesterase
  • insecticides examples include: imidacloprid, thiacloprid, clothianidin, thiamethoxam, dinotefuran, flupyradifurone, chlorantraniliprole, tetraniliprole, cyantraniliprole, pymetrozine, fipronil, ethiprole, spinosad, spinetoram, benfuracarb, carbosulfan, etofenprox, buprofezin, bensultap, cartap and spirotetramat.
  • molluscicides which may be mentioned are metaldehyde and methiocarb.
  • Herbicides or plant growth regulators which may be mentioned are:
  • MBH-024 flowable (Herbicide/Growth Regulator Test Results, Japan Association for Advancement of Phyto-Regulators).
  • Heterocyclic carboxylic acid derivates for example dichlorophenylpyrazolin-3-carboxylic acids, e.g. l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-4,5-dihydro-lH-pyrazole-3-carboxylic acid, diethyl l-(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-lH-pyrazole-3,5-dicarboxylate ("mefenpyr- diethyl”), and similar compounds known from WO 91/07874; for example dichlorophenylpyrazolecarboxylic acids, e.g.
  • R 1 represents (Ci-C6)alkyl, which is unsubstituted or mono- to trisubstituted by substituents selected from the group consisting of halogen, (Ci-C i)alkoxy, (Ci-C6)haloalkoxy and (Ci-C4)alkylthio;
  • R 2 represents halogen, (Ci-C4)alkyl, (Ci-C4)alkoxy, CF3;
  • m is 1 or 2; des of the formula (III)
  • R 3 , R 4 independently of one another represent hydrogen, (Ci-Ce)alkyl, (C3-C6)alkenyl, (C3-C6)alkynyl, (C3-C6)cycloalkyl,
  • R 3 cyclopropyl
  • R 4 hydrogen
  • R 5 n 5-Cl-2-OMe
  • R 3 ethyl
  • R 4 hydrogen
  • R 5 disturb 2-OMe
  • R 3 isopropyl
  • R 4 hydrogen
  • R 5 disturb 5-Cl-2-OMe
  • R 3 isopropyl
  • R 4 hydrogen
  • R 5 n 2-OMe. or for example benzoylsulfamoylphenylureas of the formula (IV)
  • R 6 , R 7 independently of one another represent hydrogen, (Ci-Cg)alkyl, (C3-Ce)alkenyl, (C3-C6)alkynyl, R 8 represents halogen, (Ci-C4)alkyl, (Ci-C i)alkoxy, CF3 r is 1 or 2; in particular
  • ethyl 3,4,5- triacetoxybenzoate 4-hydroxy-3,5-dimethoxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4- dihydroxybenzoic acid, 4-fluoro-2-hydroxybenzoic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid (cf. WO 2004/084631 , WO 2005/015994, WO 2005/016001).
  • l ,2-Dihydrochinoxalin-2-ones e.g. l -methyl-3-(2-thienyl)-l ,2-dihydrochinoxalin-2-one, 1 - methyl-3-(2-thienyl)-l ,2-dihydrochinoxalin-2-thione, l -(2-aminoethyl)-3-(2-thienyl)-l ,2- dihydrochinoxalin-2-one hydrochlorid, l -(2-methylsulfonylaminoethyl)-3-(2-thienyl)-l ,2- dihydrochinoxalin-2-one (cf. WO 2005/1 12630).
  • R 9 represents halogen, (Ci-C i)alkyl, (Ci-C4)haloalkyl, (Ci-C4)alkoxy, (Ci-C4)haloalkoxy, R 10 represents hydrogen or (Ci-C i)alkyl,
  • R 10 represents hydrogen, in each case unsubstituted or mono- to trisubstituted (Ci-Cg)alkyl, (C 2 -C i)alkenyl, (C 2 -C 4 )alkynyl, or aryl, where the substituents are selected from the group consisting of halogen and (Ci-Cg)alkoxy, s is 0, 1 or 2.
  • R 12 represents halogen, (Ci-C4)alkyl, methoxy, nitro, cyano, CF3, OCF3,
  • Y, Z independently represent O or S, t is 0, 1, 2, 3 or 4, R represents (Ci-Ci6)alkyl, (C 2 -C6)alkenyl, aryl, benzyl, halogenobenzyl, R 14 represents hydrogen or (Ci-C6)alkyl.
  • Oxyimino compounds known as seed treatment agents, e.g. "oxabetrinil” [(Z)-l,3- dioxolan-2-ylmethoxyimino(phenyl)acetonitril] , "fluxofenim” [ 1 -(4-chlorophenyl)-2,2,2-trifluoro- 1 - ethanone-0-(l,3-dioxolan-2-ylmethyl)-oxime], and "cyometrinil” or "CGA-43089” [(Z)-cyanomethoxy- imino(phenyl)-acetonitril], all known as seed treatment safener for sorghum against damage by metolachlor.
  • seed treatment agents e.g. "oxabetrinil” [(Z)-l,3- dioxolan-2-ylmethoxyimino(phenyl)acetonitril]
  • Isothiochromanones e.g. methyl [(3-oxo-lH-2-benzothiopyran-4(3H)- ylidene)methoxy] acetate (CAS-Reg. No. 205121-04-6) and similar compounds known from WO 98/13361.
  • JP-A 60-087254 which is known as safener for rice against damage by some herbicides
  • "methoxyphenon” or “NK 049” (3,3'- dimethyl-4-methoxy-benzophenone), which is known as safener for rice against damage by some herbicides
  • "CSB” [l -bromo-4-(chloromethylsulfonyl)benzene] of Kumiai (CAS-Reg. No. 54091 -06-4), which is known as safener for rice against damage by some herbicides.
  • safeners are dichlorophenylpyrazolin-3-carboxylic acids, e.g. l -(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-4,5-dihydro-lH-pyrazole-3-carboxylic acid, diethyl l -(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-lH-pyrazole-3,5-dicarboxylate ("mefenpyr- diethyl”), and similar compounds known from WO 91/07874.
  • Most preferred examples of safeners is mefenpyr-diethyl.
  • plant growth regulators which may be mentioned are chlormequat chlorure, chlorocholine chloride and ethephon.
  • Plant nutrients that can be given as examples include typical inorganic or organic fertilizers for supplying macronutrients and/or micronutrients to plants. Examples include nitrogenous fertilizers, phosphatic fertilizers, and potassic fertilizers, as well as fertilizers containing calcium, magnesium, sulfur, iron, trace elements, silicon, and other plant-essential elements.
  • Biopesticides that can be given as examples include yeasts and bacteria; e.g., Metschnikowia fructicola or bacillus firmus.
  • the agrochemical active ingredient a) can be set within a range of 0.05- 30 wt.%, and preferably 0.1-20 wt.%, and more preferably 0.2-10 wt.% of the granular agrochemical composition.
  • the granular agrochemical composition may contain two, three or four different active ingredients a) which could be selected from each of the four different catogeries given in Table 1.
  • the swelling agent b) in the present invention is a substance that increases in volume by absorbing water, and releases an agrochemical from inside a granular formulation as a result.
  • coating granulation involves mixing a swelling agent b) together with an agrochemical a) and bonding the mixture to the surface of granular silica sand, granular calcium carbonate, or another carrier c), or bonding the agrochemical agent a) to the surface of the carrier c) and then bonding the swelling agent b) to the surface thereof.
  • extrusion granulation involves mixing together a carrier c), an agrochemical agent a) and a swelling agent b) and molding the mixture by extruding granulation, or bonding the swelling agent b) to a granular formulation obtained by molding the carrier c) and the agrochemical agent a) by extruding granulation.
  • the swelling agent b) include bentonite, starch, glucomannan, and water- absorbent polymers.
  • Sodium bentonite is preferred as a bentonite.
  • the starch include corn starch, potato starch, methyl starch, and carboxymethyl starch.
  • water-absorbent polymers include cellulose-based polymers, polyvinyl alcohol, sodium polyacrylic acid, cross-linked polyacrylate, starch-polyacrylate, isobutylene-maleate, PVA-polyacrylate.
  • Bentonite, glucomannan, or water- absorbent polymers are preferred as the swelling agent.
  • Most preferred swelling agents are sodium bentonite, e.g. Kunigel ® VI, Kunigel ® V2, Kunipia ® G and Kunipia ® F (Kunimine Industries Co., LTD).
  • These swelling agents b) can be used independently or in a plurality, and there is no particular limitation as to the type or combination of types thereof.
  • the swelling agent b) is typically compounded in an amount of 0.1-80 wt.%, and preferably 0.2- 70 wt.% and more preferably 1-60 wt.% depending on the swelling power with respect to the total weight of the granular agrochemical composition.
  • sodium bentonite 20-60 wt.% is preferred.
  • Examples of the other formulants g) in the present invention include solid diluents.
  • Specific examples include clay, powdered pumice, burned diatomaceous earth, kaolin, talc, acid clay, calcium carbonate, and other minerals.
  • the solid diluents can be set within a range of 1-70 wt.%, and preferably 5-60 wt.%), and more preferably 10-50 wt%> with respect to the total weight of the granular agrochemical composition.
  • Examples of the other formulants g) in the present invention include binders for use in primary granules.
  • a binder can be used in order to impart a degree of hardness to the primary granules obtained from extruding granulation, or in order to mold the granular formulation as necessary.
  • Specific examples of the binder include: hydroxypropyl cellulose; carboxymethyl cellulose; PVA; and glucose, lactose, fructose, mannitol, sucrose, dextrin, and other sugars and preferably hydroxypropyl cellulose; carboxymethyl cellulose; PVA; dextrin, and more preferably carboxymethyl cellulose; and dextrin.
  • the binders can be used independently, or can be used in a combination of two or more.
  • the binder content can be set within a range of 0.1-10 wt.%, and preferably 0.2-5 wt.%, and more preferably 0.5-5 wt.% with respect to the total weight of the granular agrochemical composition.
  • Examples of the surfactant d) for use in the primary granules in the present invention selected from non-ionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants.
  • Suitable non-ionic surfactants or dispersing aids d) are all substances of this type which can customarily be employed in agrochemical agents.
  • selected classes can be optionally phosphated and neutralized with bases
  • Possible anionic surfactants d) are all substances of this type which can customarily be employed in agrochemical agents.
  • Alkali metal, alkaline earth metal and ammonium salts of alkylsulphonic or alkylphospohric acids as well as alkylarylsulphonic or alkylarylphosphoric acids are preferred.
  • a further preferred group of anionic surfactants or dispersing aids are alkali metal, alkaline earth metal and ammonium salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of alkylnaphthalene sulphonic acids, salts of naphthalenesulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, salts of polyoxyalkylene arylphenyl ether sulphonic acid, salts of polyoxyethylene dodecylether carboxylic acid, salts of alkyl sulfosuccinate and salts of lignosulphonic acid.
  • Possible amphoteric surfactants d) are all substances of this type which can customarily be employed in agrochemical agents. Aliphatic alkyl betaine and alkylammonium salt are preferred.
  • Possible cationic surfactants surfactants d) are all substances of this type which can customarily be employed in agrochemical agents. Alkylpyridinium salt and polyethylene polyamine fatty acid amide are preferred.
  • Table 3 refers to most preferred surfactants d).
  • Soprophor ® 4D384 Solvay tristyrylphenol ethoxylate (16EO) 119432-41-6 sulphate ammonium salt
  • Soprophor ® 3D33 Solvay tristyrylphenol ethoxylate (16EO) 90093-37-1 phosphate
  • Newkalgen ® FS-7S Takemoto oil Polyoxyalkylene arylphenyl ether 128282-33-7
  • Newkalgen ® FS- Takemoto oil Polyoxyalkylene arylphenyl ether 119419-11-3 700PG & fat sulphonic acid, ammonium salt
  • Newkalgen ® TG 310 Takemoto oil Polyoxyethylene alkanediol 143607-17-4
  • Atlox ® 4912 Croda block-copolymer of polyethylene
  • Further additives h) which can optionally be contained in the formulations according to the invention are penetration promoters, wetting agents, spreading agents and retention agents. Suitable are all substances which can customarily be employed in agrochemical agents for this purpose.
  • Suitable examples for additives h) are ⁇ ethoxylated branched alcohols (e.g. Genapol ® X-type) with 2-20 EO units;
  • ethoxylated coconut alcohols e.g. Genapol ® C-types
  • ethoxylated coconut alcohols e.g. Genapol ® C-types
  • ethoxylated CI 2/15 alcohols e.g. Synperonic ® A-types
  • ⁇ propoxy-ethoxylated alcohols branched or linear, e.g. Antarox ® B/848, Atlas ® G5000, Optimizamul ® HOT 5902;
  • the surfactant d) content can be set within a range of 0.005-10 wt.%, and preferably 0.01-5 wt.%, and more preferably 0.1-5 wt.% with respect to the total weight of the granular agrochemical composition.
  • hydrophobic substance f) for use in the coating examples include calcium stearate, magnesium stearate, and aluminum stearate; calcium stearate is preferred.
  • the hydrophobic-substance f) content can be set within a range of 0.5-30 wt.%, and preferably 1- 25 wt.%), and more preferably 2-20 wt.% with respect to the total weight of the granular agrochemical composition.
  • the carrier c) for use in the coating in the present invention is a chemically inert powder substance that is mixed with the hydrophobic substance f), or that can have hydrophilic properties imparted to the surface thereof after coating of the hydrophobic substance;
  • examples of the carrier c) include clay, finely powdered pumice, fired diatomaceous earth, kaolin, talc, acid clay, bentonite, and calcium carbonate. Calcium carbonate, bentonite, talc, and clay are preferred as the carrier c). It is preferred to use a mixture of carrier c) and hydrophobic substance f). Most preferred a mixture of talc and calcium stearate is used.
  • the carrier c) is coated with the binder e).
  • the binder e) according to the invention is either a polyurethane resin obtained by reacting a polyisocyanate compound and a polyol compound, or a polyurea resin obtained by reacting a polyisocyanate compound and a polyamine compound.
  • polyisocyanate compound in the present invention examples include: toluene diisocyanate (also referred to as "TDI”); diphenylmethane diisocyanate (also referred to as "MDI"), polymethylene polyphenyl polyisocyanate (polymeric MDI), xylylene diisocyanate (XDI), and other aromatic polyisocyanates; hexamethylene diisocyanate (HDI), and other aliphatic polyisocyanates; isophorone diisocyanate (IPDI), 1 ,4-cyclohexyldiisocyanat (CHDI), and other alicyclic polyisocyanates; as well as mixtures thereof.
  • Preferred polyisocyanate compounds in the present invention are MDI- and HDI-based polyisocyanates.
  • polyol compound in the present invention examples include polyether polyols, polyester polyols, polybutadiene polyols, polycarbonate polyols, polycaprolactone polyols, polysulfide polyols, natural oil polyols e.g. castor-oil-based (triglyceride-based) polyols, as well as mixtures thereof.
  • Preferred polyol compound in the present invention are polyether polyols (e.g. Toho polyol PE-555) and castor-oil-based (triglyceride-based) polyols.
  • polyamine compound in the present invention examples include: hexamethylene diamine (HMD), diethylene triamine (DETA), triethylene tetramine (TETA), polyaspartic acid esters and other aliphatic polyamines, diethyl toluylene diamine, 4,4-methylene-bis(2-chloro aniline) (MbOCA) and other aromatic amines as well as mixtures thereof.
  • HMD hexamethylene diamine
  • DETA diethylene triamine
  • TETA triethylene tetramine
  • polyaspartic acid esters and other aliphatic polyamines diethyl toluylene diamine
  • MbOCA 4,4-methylene-bis(2-chloro aniline)
  • Preferred polyamine compound in the present invention are polyaspartic acid esters.
  • the binder e) content can be set within a range of 0.1-10 wt.%, and preferably 0.2-5 wt.%, and more preferably 0.5-5 wt.% with respect to the total weight of the granular agrochemical composition.
  • the binder e) is added such that the total amount thereof does not exceed the amount of the hydrophobic substance f) or the carrier c).
  • An appropriate amount should be coated because aggregation occurs when the amount of the binder e) is too high, and the hydrophobic substance f) and the carrier c) are not sufficiently coated when the amount of the binder e) is low.
  • the binder e) can be added in an order such that: the polyisocyanate is added after the polyol or polyamine is added; the polyisocyanate is added before the polyol or polyamine is added; or the polyol or polyamine and the polyisocyanate are added at the same time separately or after having been mixed together in advance.
  • OH equivalent weight of the polyol or polyamine used in the present invention a value within a range of 50-1000, and preferably 100-700 and more preferably 100-400, can be selected.
  • NCO equivalent weight of the polyisocyanate used in the present invention a value within a range of 50-1,000, and preferably 100-700, and more preferably 100-400 can be selected.
  • the primary granules according to the present invention are prepared by: granulating a mixture of an agrochemical active ingredient a), a swelling substance b), and, depending on the circumstances, a carrier c), and a surfactant d), and the other formulants g) using an extruding granulator; sizing and forming the primary granule into spheroids using a spheronizer; and performing drying. It is unnecessary for the primary granules to be perfectly spheroidal; long primary granules are also permitted.
  • the hydrophobic substance f) or a mixture of the hydrophobic substance f) and the carrier c) is coated on the surface using the binder e).
  • the binder e) is added such that the amount thereof does not exceed that of the hydrophobic substance f) and such that aggregation does not occur. Optimizing the amount of the binder e) makes it possible to maintain the flowability of the primary granules and avoid aggregation, resulting in a high recovery rate. Maintaining the flow properties obviates the need for heating in the coating step.
  • Such "powder coating” can be performed using powder coating-granulation through a tumbling- or centrifugal-tumbling-type granulator/mixer.
  • coating may be performed in continuation using the carrier c).
  • optimizing the amount of the binder e) makes it possible to maintain the flowability of the granules and avoid aggregation, resulting in a high recovery rate.
  • Optimizing the mixing ratio of the binder e) and the carrier c) obviates the need for heating in the coating step. There are also cases when heating is performed after coating, as necessary, using a temperature and period of time that are sufficient for forming polyurethane or polyurea.
  • the timed-release-type granular agrochemical composition of the present invention can control the amount of agrochemical active ingredients a) released from the composition to 0% or less than 5 % of the whole amount of that in the composition in the period in which releasing of the ingredients is suppressed, after an application of the composition and, in the following period in which the ingredients is released, can start releasing the agrochemical active compound at the same time of the breakup of the surface of the composition by swelling of the primary granules and can immediately release the ingredients.
  • the release curve of the agrochemical active ingredients a) of the timed-release-type granular agrochemical composition of the present invention is observed as like sigmoid type's curve as a whole.
  • the length of the aforementioned period in which releasing of the compounds is suppressed and the following period in which the compound is released can be occasionally configured by changing species and/or amount of an agrochemical active compound, a swelling substance, a surfactant, a carrier, a binder, a hydrophobic substance and the other formulants according to the purpose of use of and using conditions of the timed-release-type granular agrochemical composition of the present invention.
  • the length of the aforementioned period in which releasing of the ingredient is suppressed may be occasionally configured to, for examples, the period within 60 days after the application of the composition, or within 30 days, 10 days, 5 days or 3 days.
  • the length of the aforementioned period in which the ingredient is released may be occasionally configured to, for examples, the period within 90 days, or within 60 days, 30 days, 20 days, 10 days, 5 days or 3 days.
  • inventive compositions have potent microbicidal activity and can be used for control of unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • the invention also relates to a method for controlling unwanted microorganisms, characterized in that the inventive active ingredients are applied to the phytopathogenic fungi, phytopathogenic bacteria and their habitat.
  • Fungicides can be used in crop protection for control of phytopathogenic fungi. They are characterized by an outstanding efficacy against a broad spectrum of phytopathogenic fungi, including soilborne pathogens, which are in particular members of the classes Plasmodiophoromycetes , Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes , Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi imperfecti). Some fungicides are systemically active and can be used in plant protection as foliar, seed dressing or soil fungicide. Furthermore, they are suitable for combating fungi, which inter alia infest wood or roots of plant.
  • Bactericides can be used in crop protection for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include: diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, for example Puccinia recondite, P.
  • diseases caused by powdery mildew pathogens for example Blumeria species, for example Blumeria graminis
  • Uromyces species for example Uromyces appendiculatus
  • diseases caused by pathogens from the group of the Oomycetes for example Albugo species, for example Algubo Candida
  • Bremia species for example Bremia lactucae
  • Peronospora species for example Peronospora pisi or P.
  • Urocystis species for example Urocystis occulta
  • Ustilago species for example Ustilago nuda, U. nuda tritici
  • Botrytis species for example Botrytis cinerea
  • Penicillium species for example Penicillium expansum and P.
  • Sderotinia species for example Sderotinia sderotiorum
  • Verticilium species for example Verticilium alboatrum
  • seed and soilborne decay, mould, wilt, rot and damping-off diseases caused, for example, by Alternaria species, caused for example by Alternaria brassidcola
  • Aphanomyces species caused for example by Aphanomyces euteiches
  • Ascochyta species caused for example by Ascochyta lentis
  • Aspergillus species caused for example by Aspergillus flavus
  • Cladosporium species caused for example by Cladosporium herbarum
  • Cochliobolus species caused for example by Cochliobolus sativus
  • Plasmodiophora species for example Plamodiophora brassicae
  • diseases caused by bacterial pathogens for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae
  • Pseudomonas species for example Pseudomonas syringae pv. lachrymans
  • Erwinia species for example Erwinia amylovora.
  • phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregular e, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sderotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
  • inventive fungicidal compositions can be used for curative or protective/preventive control of phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • inventive active ingredients or compositions which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • the fact that the active ingredients are well tolerated by plants at the concentrations required for controlling plant diseases allows the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
  • plants and plant parts can be treated.
  • plants are meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights).
  • Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods.
  • plant parts are meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed.
  • Crops and vegetative and generative propagating material for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
  • inventive active ingredients when they are well tolerated by plants, have favourable homeotherm toxicity and are well tolerated by the environment, are suitable for protecting plants and plant organs, for enhancing harvest yields, for improving the quality of the harvested material. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some stages of development.
  • Plants which can be treated in accordance with the invention include the following main crop plants: maize, soya bean, alfalfa, cotton, sunflower, Brassica oil seeds such as Brassica napus (e.g. canola, rapeseed), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, Arecaceae sp. (e.g. oilpalm, coconut), rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, nuts, grapes and vine and various fruit and vegetables from various botanic taxa, e.g. Rosaceae sp. (e.g.
  • pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds, plums and peaches, and berry fruits such as strawberries, raspberries, red and black currant and gooseberry), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp. (e.g. olive tree), Actinidaceae sp., Lauraceae sp. (e.g. avocado, cinnamon, camphor), Musaceae sp. (e.g.
  • Rubiaceae sp. e.g. coffee
  • Theaceae sp. e.g. tea
  • Sterculiceae sp. e.g. lemons, oranges, mandarins and grapefruit
  • Solanaceae sp. e.g. tomatoes, potatoes, peppers, capsicum, aubergines, tobacco
  • Liliaceae sp. Compositae sp. (e.g. lettuce, artichokes and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (e.g.
  • Cucurbitaceae sp. e.g. cucumbers - including gherkins, pumpkins, watermelons, calabashes and melons
  • AUiaceae sp. e.g. leeks and onions
  • Cruciferae sp. e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage
  • Leguminosae sp. e.g. peanuts, peas, lentils and beans - e.g. common beans and broad beans
  • Chenopodiaceae sp. e.g.
  • compositions according to the invention covers a broad weed spectrum which is specific in particular for rice crops.
  • genera such as, for example, Echinochloa spp., Panicum spp., Poa spp., Leptochloa spp., Brachiaria spp., Digitaria spp., Setaria spp. Cyperus spp.
  • Echinochloa oryzicola Monochoria vaginalis, Eleocharis acicularis, Eleocharis kuroguwai, Cyperus difformis, Cyperus serotinus, Sagittaria pygmaea, Alisma canaliculatum, Scirpus juncoides.
  • the activity spectrum extends to genera such as, for example, Polygonum spp., Rorippa spp., Rotala spp., Lindernia spp., Bidens spp., Sphenoclea spp., Dopatrium spp., Eclipta spp., Elatine spp., Gratiola spp., Lindernia spp., Ludwigia spp., Oenanthe spp., Ranunculus spp., Deinostema spp..
  • the present invention furthermore provides a method for the selective control of unwanted plants, preferably in crop plants, in particular in rice crops (planted or sown under upland or paddy conditions using indica or japonica species and/or hybrids/mutants/GMOs), which comprises applying the composition according to the invention to the plants (for example harmful plants, such as monocotyledonous or dicotyledonous broad-leaved weeds, weed grasses, Cyperaceae or unwanted crop plants), the seed (for example grains, seeds or vegetative propagation organs, such as tubers or shoot parts with buds) or to the area in which the plants grow (for example the area under cultivation, which may also be covered by water), for example together or separately.
  • the herbicides may be applied before, after or simultaneously with the other herbicide to the plants, the seed or the area in which the plants grow (for example the area under cultivation).
  • Unwanted plants are to be understood as meaning all plants which grow in locations where they are unwanted. These can, for example, be harmful plants (for example monocotyledonous or dicotyledonous weeds, weed grasses, Cyperaceae or unwanted crop plants), including, for example, those which are resistant to certain herbicidally active compounds, such as glyphosate, glufosinate, atrazine, imidazolinone herbicides, sulfonylureas, (hetero)aryloxyaryloxyalkylcarboxylic acids or phenoxyalkylcarboxylic acids ('fops'), cyclohexanedione oximes ('dims') or auxin inhibitors.
  • harmful plants for example monocotyledonous or dicotyledonous weeds, weed grasses, Cyperaceae or unwanted crop plants
  • certain herbicidally active compounds such as glyphosate, glufosinate, atrazine, imi
  • composition according to the invention is employed selectively for controlling unwanted vegetation, for example in crop plants such as farm crops, for example monocotyledonous farm crops, such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), or dicotyledonous farm crops, such as sugar beet, sugar cane, oilseed rape, cotton, sunflowers and leguminous plants, for example of the genera Glycine (for example Glycine max. (soybean), such as non-transgenic Glycine max. (for example conventional cultivars, such as STS cultivars) or transgenic Glycine max.
  • Glycine for example Glycine max. (soybean)
  • non-transgenic Glycine max. for example conventional cultivars, such as STS cultivars
  • transgenic Glycine max for example in crop plants such as farm crops, for example monocotyledonous farm crops, such as cereals (for example wheat, barley, rye, oats,
  • RR- soybean or LL-soybean for example RR- soybean or LL-soybean and crossbreeds thereof
  • Phaseolus, Pisum, Vicia and Arachis or vegetable crops from various botanical groups, such as potato, leek, cabbage, carrot, tomato, onion, in fruit plantations (plantation crops), greens, lawns and pasture areas, or on non-crop areas (for example squares of residential areas or industrial sites, rail tracks) in particular in rice crops (planted or sown under upland or paddy conditions using indica and japonica varieties and also hybrids/mutants/GMOs).
  • various botanical groups such as potato, leek, cabbage, carrot, tomato, onion, in fruit plantations (plantation crops), greens, lawns and pasture areas, or on non-crop areas (for example squares of residential areas or industrial sites, rail tracks) in particular in rice crops (planted or sown under upland or paddy conditions using indica and japonica varieties and also hybrids/mutants/GMOs
  • the application is preferably carried out both prior to the emergence of the harmful plants and to the emerged harmful plants (for example broad- leaved weeds, weed grasses, Cyperaceae or unwanted crop plants), independently of the stage of the sown/planted crop.
  • the harmful plants for example broad- leaved weeds, weed grasses, Cyperaceae or unwanted crop plants
  • the invention also provides the use of the composition according to the invention for selectively controlling unwanted vegetation, preferably in crop plants, in particular in rice crops (planted or sown under upland or paddy conditions using indica and japonica varieties and also hybrids/mutants/GMOs).
  • unwanted vegetation preferably in crop plants, in particular in rice crops (planted or sown under upland or paddy conditions using indica and japonica varieties and also hybrids/mutants/GMOs).
  • the present invention is exemplified by the following embodiment; however, this embodiment is not given by way of any limitation.
  • Examples 1-5 (according to the invention) Agrochemical active ingredients, bentonite (Kunigel ® V2), clay (NK-300), lignin (Borresperse ® NA) were uniformly mixed with the ratio given in the Table 1. Water was added to the mixture, which was kneaded, and a dome granulator was used to granulate the kneaded mixture. The granulated substance was sized and formed into spheroids using a spheronizer. After drying at 80°C, the substance was sieved to a granular size of 0.85-1.7 mm to yield primary granules. [0140] Table 1 : Examples 1 to 10, Comparative Examples
  • Table 1 continue Total 100.00 100.00 100.00 100.00 100.00 100.00
  • Bentonite Kunigel ® V2
  • clay NK-300
  • lignin Borresperse ® NA
  • primary granules were prepared with the same manner to Example 1-5.
  • a polyamine (Desmophen ® NH1220; OH equivalent weight: 230), calcium stearate, an aliphatic polyisocyanate (Desmodur ® XP 2840; NCO equivalent weight: 183 or Desmodur ® N3600; NCO equivalent weight: 183), and calcium stearate were gradually added in the stated order to the resulting primary granules, and this process was repeated.
  • a polyamine, talc, an aliphatic polyisocyanate, and talc were gradually added in the stated order, and this process was repeated to form an outermost layer.
  • Examples 8 and 9 Agrochemical active ingredients are not used. Bentonite (Kunigel ® V2), clay (NK-300), lignin (Borresperse ® NA) were uniformly mixed with the ratio given in the Table 1. Thereafter primary granules were prepared with the same manner to Example 1-5.
  • a polyol (Toho ® polyol PE-555; OH equivalent weight: 137 or URIC ® Y-403; OH equivalent weight: 356) and an aliphatic polyisocyanate (Desmodur ® XP 2840; NCO equivalent weight: 183) were mixed with the ratio of 1.3: 1.7 or 2: 1, respectively (Table 1).
  • Bentonite Kunigel ® V2
  • clay NK-300
  • lignin Borresperse ® NA
  • primary granules were prepared with the same manner to Example 1-5.
  • a polyol Toho ® polyol PE-555; OH equivalent weight: 137
  • calcium stearate an aromatic polyisocyanate
  • Hycel ® 360P an aromatic polyisocyanate
  • talc talc
  • Example 2 An attempt was made to perform the same coating process as that in Example 1 without using calcium stearate or talc; however, the granules aggregated during coating, and could not be prepared.
  • Coating was performed using a water-dispersed polyurethane (Superflex ® 860, solid content 40%) instead of polyol and polyisocyanate.
  • Superflex ® 860 solid content 40%
  • the timed-release-type granular agrochemical composition according to the present invention was immersed in water, and was defined as a simple sustained-release agrochemical composition when Rl > 25%, and as a timed-release-type granular agrochemical composition when Rl ⁇ 25% (or preferably Rl ⁇ 20%), where Rl is the release rate at time T/2, and T is the time until the release rate of the agrochemical active ingredient reaches 50% after the water immersion (see Figure 1).
  • compositions of embodiment 1 and Comparative Example 2 50 mg of each of the compositions of embodiment 1 and Comparative Example 2 was treated in a release testing device (Hi-PACK; manufactured by Entec Inc.) into which 1,250 mL of tap water had been introduced, and unless otherwise stated the composition samples were maintained at 25°C. Over time, the agrochemical-active-ingredient concentration in the water was measured by liquid chromatography, and the concentration in the water was calculated.
  • Hi-PACK manufactured by Entec Inc.
  • Example 2 As indicated in Figure 2, clear timed release of the active ingredient was achieved in Example 1. The release rate Rl after the eleventh day, which is T/2, was less than 20%, indicating a sufficient timed-release effect. However, in Comparative Example 2, talc was used instead of calcium stearate, but no release control was evidenced at all.
  • the timed-release-type granular agrochemical composition of the present invention can be manufactured using a tumbling- or centrifugal-tumbling-type granulator/mixer having no heating function. Furthermore, it is possible to reduce costs by using a large-scale tumbling-type granulator/mixer (e.g. a concrete mixer or a Manson mixer) that is typically used in agrochemical manufacturing, the granulator/mixer having no heating function.
  • a large-scale tumbling-type granulator/mixer e.g. a concrete mixer or a Manson mixer

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Abstract

La présente invention concerne une composition agrochimique granulaire de type à libération lente formée par revêtement de granules primaires qui comprennent une composition mixte contenant un principe actif agrochimique, une substance de gonflement, un tensioactif et, en fonction des circonstances, les autres agents de formulation ; les granules primaires étant revêtus d'une composition mixte contenant un liant, une substance hydrophobe, un support et, en fonction des circonstances, les autres agents de formulation.
PCT/EP2017/059430 2016-04-28 2017-04-20 Composition agrochimique granulaire de type à libération lente et son procédé de fabrication WO2017186577A1 (fr)

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US16/096,608 US20190133118A1 (en) 2016-04-28 2017-04-20 Time-release-type granular agrochemical composition and method for manufacturing same
CN201780040718.5A CN109310082B (zh) 2016-04-28 2017-04-20 定时释放型颗粒状农用化学组合物及其制造方法
JP2018556436A JP7204486B2 (ja) 2016-04-28 2017-04-20 徐放型顆粒状農薬組成物およびその製造方法
KR1020187034410A KR102538200B1 (ko) 2016-04-28 2017-04-20 시한―방출―유형 과립상 농약 조성물 및 이것의 제조 방법
PH12018502244A PH12018502244A1 (en) 2016-04-28 2018-10-19 Timed-release-type granular agrochemical composition and method for manufacturing same

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RU2767635C1 (ru) * 2021-06-29 2022-03-18 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Комплексный препарат для предпосевной обработки семян яровой пшеницы на основе гиббереллинов, полиэтиленгликоля и фруктозы

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PH12018502244A1 (en) 2019-08-19
TWI756220B (zh) 2022-03-01
US20190133118A1 (en) 2019-05-09
CN109310082B (zh) 2022-03-29
TW201806483A (zh) 2018-03-01
JP2019515928A (ja) 2019-06-13
EP3238540A1 (fr) 2017-11-01
CN109310082A (zh) 2019-02-05
KR20180135970A (ko) 2018-12-21
KR102538200B1 (ko) 2023-05-30

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